Emulsion



Patented July 11, 1933 BENJAMIN R. HARRIS, OF CHICAGO, ILLINOIS EMULSION No Drawing. Application filed August 21, 1980, Serial No. 476,935. Renewed October 5, 1 982.

My invention relates in general to improved emulsions and emulsion lmproving substances. It relates more specifically to an improved non-spattering type of margarine and anti-spattering substances for use with margarine. I

By means of my new products I am able to impart superior qualities to many. types of emulsions, particularly emulsions of fats and oils'used for culinary purposes, but I shall explain the same in connection with improvements in margarine. Those skilled in the art are referred to my prior application Serial Number 383,143, filed on August 2, 1929, for a more complete disclosure of certain details of the invention than is made herein. I wish also to call attention to my co-pending application Serial Number 47 5,622, filedon August 15, 1930, as a continuation in part of application Serial Number 383,143, filed August 2, 1929.

In general the present invention represents a specific embodiment of the main invention disclosed in the co-pending application above referred to, and while the present disclosure is substantially complete in so far as it describes the invention and supports the claims, those interested in the art are referred to the co-pending case for a more complete disclosure of the basic conce t of the invention.

The principal object o my present invention is to improve such forms of emulsion as margarine.

Another object is to reduce the spattering of margarine when used for frying purposes and generally improve its frying behavior.

Other objects and features of the invention will be apparent from a consideration of the following detailed description.

As was disclosed in my prior applications I have discovered a large class of chemical compounds which may be used to impart improved characteristics to all types of wateroil emulsions, particularly those used for cooking purposes, and other types of culinary fat preparations. These substances have several characteristics in common which make them very valuable in their use with margarine. These substances are compatible with mild acids and in particular with lactic acid in the concentration and under the conditlons existing in margarine. They are dlfiic-ultly soluble in oils and fats and aqueous media and in many cases are substantially frying temperatures and so will remain in the margarine and during frying.

One of the most important characteristics of these compounds is the presence in the molecule of two types of groups in balanced relation to each other, one group being hydrophyllic or water wetting in character, and the other group being lipophyllic or fat wetting in character. These groups must exist in the molecule in such a state of balance that they will function at the water-oil interface in the intended manner. Presumably these substances orientate themselves at the interface, by reason of the balance of the two types of groups, but it is understood that the invention does not depend upon this explana- My prior application treats exhaustively of the manner in which the balance between the two groups may be determined so that without tests of any kind it is possible for the skilled colloid chemist to pick out compounds which can not function effectively as anti-spatterers, as well as compounds which clearly will be effective as anti-spatterers.

However, there are compounds of such character that the state of balance existing between the two groups in the molecule is preferably determined by a simple quick test.

The balance of the hydrophile-lipophile groups in the compound which I apply in my invention is one of the characteristics and determinant of the class of substances which I employ.

perform their function The test which I have chosen as a means for determining the hydrophile-lipophile balance in organic compounds, I call the spoon test. It is carried out as follows: From 0.05 to 0.10 gr. of the material or substance in question is introduced into a porcelain mortar, wetted and ground into a smooth paste with a pestle with a minimum proportion of water; two to five drops generally will suffice.

An ordinary margarine such for example as one made from vegetable oils, and fats and cultured skimmed milk and which possesses the usual property of spattering during frying is selected. Ten grams of this margarine are then introduced in small portions into the mortar and macerated thoroughly with the paste first prepared until the entire ten gram portion is thoroughly and uniformly intermixed with the material in the mortar. Two grams of this mixture are introduced into a tablespoon and held direct- 1y over a free flame such for example a Bunsen flame, one or two inches long, in such a position that the point of the flame just about reaches the bottom of the spoon. A clean sheet of paper is placed on the bottom of the burner by inserting the stem of the Bunsen burner prior to lighting through a hole made in the center of the paper and a1 lowing the paper to dropto the base of the burner to catch the margarine splashed out during the heating. The mixture in the spoon is heated until all of the water is boiled off and the ebullition ceases and the spots on the paper observed.

If this treated margarine spots the paper to the same extent as the untreated margarine from which the former was prepared, then the lipophile and hydrophile groups of the compound are not balanced. The number and size of spots on the paper or the added weight can be readily determined.

If the increase in weight of the paper or the number and character of the spots produced on the paper up until all the water has boiled off are less than that produced by similarly heating two grams of the original untreated margarine employed for the test, then the material or substance in question has balanced hydrophile-lipophile groups. The expression balanced lipophile and hydrophile groups used in the claims is to be interpreted in terms of the above described spoon test.

My present invention relates to a specific class of compounds in which the hydrophile function is exercised primarily by a phosphatic group, that is, a group containing phosphorus in the form of its oxygenated acid radicals. Preferably, the anti-spattering compounds of the present invention are entirely non-nitrogenous, but if they contain any nitrogenous group, it should be devoid of the nitrogenous linkage expressed in the following formula:

wherein O? represents oxygen, X stands for phosphorus in the form of its oxygenated acid radicals such as phosphorus, etc., C represents carbon, H is hydrogen, w represents a small Whole number, and N is trivalent or pentavalent nitrogen and the terminal oxygen indicated above is linked directly to carbon.

In my co-pending application, Serial No. 481,348 filed September 11, 1930, I describe and claim certain types of nitrogenous compounds which can be used with my invention. In my present application I am interested principally in compounds containing phosphorus.

Examples of some of the phosphatic materials which I have used as anti-spattering agents, many of them not known heretofore, are as follows:

ll C1 H450--POH (Monocholesteryl dihydrogen orthophosphate) C21H4s-0 O P (Dicholesteryl hydrogen orthophosphate) 0 CHr-(CHzM-CHP O--i OH (Caryl dihydrogen orthophosphate) CnHu--O-Oflz- CH1 0CHzOH:- 0i 0H (Stearyl diethyleue glycol dihydrogen orthophosphate) Calcium triricinolein phosphite lipophile groups, but'which nevertheless are not anti-spatterers are as'follows:

Glass A In the case of compounds of both Class A and GlassB, anti-spattering powers are lacking because of inadequate balance between the lipophile In the case of compounds of Class A, the hydrophile group dominates and is inadequately balanced by the lipophile group, that IS, the lipophile characteristics of the latter are too weak to balance and coact with the hydrophile group. In the case of substances of Class B, the reverse situation exists and power is absent because the anti-spattering lipophile group is dominant and is inadequately balanced by the hydrophile group. The examples of phosphatic anti-spatterers listed above, as well as other phosphatic substances which can be employed for the purpose which I have used successfully, I prepared by a 'number of difierent methods which are adeo uately described in the scien.

tific and technical literature, and which and hydrophile groups.

methods are readily available to skilled chemists.

The compounds described above are-of unusual importance in connection with their use with water-oil emulsions of all kinds, but

they have a particular adaptation for use with all culinary emulsion products such as margarine. Commercial margarine after being treated with my anti-spattering agent, when fried ina shallow pan exhibits improved frying behavior in that it allows i s water to boil ofi' quietly, fries in a pleasing and comparatively quiet manner with the formation of considerable turbid froth and foam after the manner of butter, reduces the i ,tendency of the curd to stick to the bottom of the frying pan, and reduces the amount of material which escapes from the pan by spattering. Untreated margarine on the other hand when fried bumps turbulently, sputters i noisily and foams comparatively little. Also what little foam there is, is transparent and of an entirely different character from that obtained from margarine with an anti-spatterer.

My emulsion improvers may be introduced in the margarinein a numberof ways, as long as a satisfactory dispersion is obtained. For

previously treated instance, the main constituents of margarine are edible oils and fats and cultured milk, and 9 the anti-spattering or improving compounds may be introduced either into the oils or milk .in any suitable manner. They may also be introduced into the churn during the production-of the emulsion in its liquid state, care 1 being taken to bring about the necessary dispersion. Or, the -anti-spattering material may be used in a dry condition and mixed with the salt which is worked into the crystallized margarine, or the anti-spattering 1 material may be made into a paste with milk and kneaded in, or blended into the margarine.

Generally speaking, the compounds which I am using in connection with this invention 1 arez'Phosphoric acid esters of high molecular weight organic compounds which will balance the phosphoric acid radical. It is to be noted that in each case the hydrophile group containing phosphorus is at or near an 1 end of the molecule. These compounds may be represented structurally as follows R-O-IF-O- X 11 YO w in which 0 is oxygen, P is phosphorus, X is an edible cation such as hydrogen, sodium, potassium, calcium, or the like, Y H is either'an edible cation or an organic radical, ii w is a small whole number and R is. an organic lipophile group.

Thus, the above compounds may be phosphoric acid esters of a high molecular alcohol 12 uch as cctyl alcohol, or it may be a phosphoic acid ester of a polyalcohol and/or its subtitution products such as, for example, a hosphoric acid ester of glycol or diethylene dycol in which one OH is esterified with a iigher fatty acid such as stearic acid, or comincd in an ether linkage with a high alcohol uch as cholesterol. Thus, for example, a bllOSPllOllC acid ester of stearyl diethylene lycol, a phosphoric acid ester of monostearyl 'lycerol, or a phosphoric acid ester of choleseryl-diethylenc glycol.

As to the specific application of the inention to margarine and other emulsions or leaginous culinary preparations, it is clear hat since there are many phosphatic coinounds containing balanced hydrophile and pophile groups, it is impractical and unecessary to list each particular combination f groups which can be used in accordance it-h my invention. Moreover, while I leave )mething to the skill of persons applying iy invention, my description is Wholly suffiently exhaustive, particularly when consid-v red with respect to my prior applications, enable those skilled in the art to success illy practise the same.

The term non-spattering margarine as sed in the claims is employed to designate a .argarine, the frying behavior of which is iproved by the addition thereto of the nov el materials of my invention herein described. The term margarine as employed in the claims includes plastic emulsions of vegetable or animal oleaginous substances or mixtures thereof, with aqueous materials such as water, sweet or ripened milk, and with or Without coloring matter. Examples of margarine within this definition, besides the conventional margarine of commerce, are: puif paste, renovated butter, and any like fatty-aqueous compositions which may be used in frying.

What I claim is new and desire to protect by Letters Patent of the United States is 1. A non-spattering margarine, having an oleaginous p ase and an aqueous phase, and having included therein a proportion of a phosphoric acid ester of a higher molecular weight alcohol having eighteen carbon atoms or more in its radical, said compound having balanced hydrophile and lipophile groups.

2. A non-spatt'ering margarine, having an olea-ginous phase and an aqueous phase, and having included therein a proportion of a chemical substance having a lipophile group in the form of a cholesteryl radical, and a balancing hydrophile group containing phosphorus.

In witness whereof I hereunto subscribe my name this 18th day of July, 1930.

BENJAMIN R. HARRIS. 

